Benzacridonyl anthraquinone dyestuff



Patented Apr. 6, 1943 UNITED STATES PATENT OFFICE BENZACRIDONYL ANTHRAQUINGNE DYESTUFF Alfred Miller, Orchard P Allied Chemical & D

tion of New York ark, N. assignor to ye Corporation, a corpora- NoDrawing. Application December 2, 1938; Serial NO. 243,521

pared by a number of different methods which are summarized as follows:

One molecular proportion of l-aminoanthraquinone is condensed with onemolecular proportion of 1,5-clich1oranthraquincne to formS-chlorl,l'-dianthrimide. A molecular proportion of the latter is thencondensed with one molecular proportion of l,2-benzacridonyl5-aminoanthraquinone to form the benz'acridonyl trianthr-imiderepresented by the formula:

r as l l on on do c u 1 u NH O If 1,5-dichloranthraquinone used above isreplaced by LB-dichIoranthraquinone, the benzacridonyl trianthrimideformed may be represent by the formula:

0 NH 0 NH 0 II I! II III m 00 Y I .NI-I 0 o 0 If in the above methodsthe 1,2-benzacridonyl- 5-aminoanthraquinone is replaced by1,'2-benza'cridonyl-8-amino-anthraquinone, the respective compoundsobtained may be represented by the following formulae:

The same compounds are obtained if in the above general methodsdichloranthraquinone is replaced by dibromanthraquinone. They are alsoobtained if the l-halogen-anthraquinone and the 5- or8-halogenated-1,2-benzacridonyl-anthraquinone are reacted with 1,5- orLS -diaminQanthraquinone; that is to say, if in the reactant organiccompounds of the above methods, the halogen and amino substituents areinterchanged.

Mixtures of such benzacridonyl trianthrimides result from the use of 'amixture of 1,2-benzacridonyl-5 and 8-aminoanthraquinones and/or amixture of 1,5- and 1,8-dihalogenated anthraquinones.

The foregoing benzacridonyl trianthrimides, which are the subject of mycopending application Serial No. 434,377 filed March 12, 1942, whenground yield brown violet to Bordeaux-brown powders which are sparinglysoluble in nitrobenzone but dissolve readily in concentrated sulfuricacid to form yellow-brown to orange brown to reddish brown solutionwhich, on dilution with water, precipitates the compounds as violet-redto red-violet flocks. Y

The vat dyestuffs of the present invention are obtained when theforegoing benzacridoriyl trianthrimides are condensedby the action ofacidic ring closing condensing agents; such as anhydrous aluminumchloride, ferric chloride, zinc chloride, etc. The chemical constitutionof these condensation products is not certainly known. While itisbelieved they are probably carbazols formed by joining of the twobetacarbon atoms next to an imino bridge to form the carbazol ring, theinvention is not limited to any theoretical explanation.

The iollowing'examples, in which parts are'by weight and temperaturesare in degrees centigrade, illustrate the invention:

Example 1.A mixture of 83 parts of 1,5-dicloranthraquinone, 67 parts ofl-aminoanthraquinone, 2000 parts of nitrobenzene, 100 parts of soda ash,and 10 parts of copper carbonate is raised to a temperature of 200 to210 while thoroughly agitated. It is maintained at that temperature for2 to 3 hours then after it is allowed to cool to about 130, 102 parts of1,2-benzacridonyl 5 aminoanthraquinone are added thereto, and themixture is heated to 204 to 210, where it is maintained for about 12hours. mixture is then cooled, and steam-distilled to removenitrobenzene therefrom. The resulting slurry is filtered; thefilter-cake is washed with hot water until it is free from alkali, andfinally it is dried at 100 to 110.

The final product is 1,2'-benzacridonyl-5,5', 1',1-trianthrimide. Whenground, for example to pass through a 60 mesh screen, it is a darkbrownviolet powder which dissolves in concentrated sulfuric acid to form anorange-brown solution. The latter when diluted with water deposits theproduct as red-violet flocks.

The foregoing reaction can be illustrated by the following formulae:

0 Cl U H in CeHaNOz as Solvent OuCO3+Na2CO3 \l u 0 N32 Cl 0 O 0 Cl H !iO NH O O 0 01 H H I m NH O 0 NH oo n CuH5NO2 Solvent C110 H- aCOs if ias r A Oi I II 0 NH 0 o 1,2-benzacridonyl-5,5,l,l-triantl1rimide Example2.--A mixture of 1 part of common salt and 5 parts of anhydrous aluminumchloride is fused by heating to between 120 and 130 and is thoroughlyagitated while 1 part of 1,2-benzacridonyl-5,5', 1',1-trianthrimide (seeExample 1) is gradually added thereto. The resulting melt is heated tobetween 155 and 165 and is maintained there for half an hour. The massis then transferred into 50 to 100 parts of water; the resulting slurryis boiled and. filtered; the filter cake of product, suspended in about60 parts of about 3% aqueous sulfuric acid, is again boiled; the acidslurry is filtered and the filter cake is then similarly boiled andseparated from The a boiling aqueous 5% solution of caustic soda.Finally the filter cake, after being washed with hot water until thewashings are neutral, is dried in an oven at about The dry product whenground yields a dark, almost black powder, which is very sparinglysoluble in organic solvents, but dissolves in concentrated sulfuric acidto yield a violet-brown solution which when diluted with water depositsthe dyestuff as yellow-brown flocks. From vats, the dyestuif dyes cottonyellowish-brown shades of excellent fastness to washing, light,chlorine.

The ring closing condensation of any of the other 1,2-benzacridonyltrianthrimides herein disclosed, in the form of single compounds ormixtures, can be obtained by following this procedure.

Example 3.--A condensation fusion is conducted in the manner describedin Example 2, but the final fusion temperature is maintained between and(instead of to The dyestuff thus obtained dissolves, in concentratedsulfuric acid to form a violet-brown solution, which on dilution withwater deposits the color as Bordeaux-red flocks. From vats, the dyestuffdyes cotton reddish-brown shades of excellent fastness to washing,chlorine, and light.

Example 4.--1 part of common salt, 5 parts of anhydrous aluminumchloride, and 1 part of 1,2- benzacridonyl 4benzoylamino-5,l,5',1"-trianthrimide are mixed thoroughly, andmaintained between 90 and 100 for two hours. The fusion mass is drownedin water; the slurry is filtered; and the organic filter cake isreslurried with dilute hot aqueous soda solution, again separated byfiltration, and washed alkali-free with hot water. The netural cake isdried in air at about 100 and ground. The dry powder is almost black,and dissolves in concentrated sulfuric acid to form a reddish-brownsolution which on dilution with water deposits the dyestuff asreddish-brown flocks.

In the foregoing Example 1, if 1,2-benzacridonyl-5-aminoanthraquinone isreplaced by an equal amount of l,2-benzacridonyl-8-aminoanthraquinone,the final product is 1,2-benzacridony1-8,5, 1',1-trianthrimide (FormulaIV). The 1,5-dich1oranthraquinone can be replaced by1,5-dibromanthraquin0ne.

If 1,5-dichloror dibrom-anthraquinone is replaced by 1,8-dichlorordibrom-anthraquino-ne in the foregoing reactions, the respectiveproducts are: 1,2-benZacridony1-5, or 8, 1,8,1"-tri anthrimides(Formulae III and V). Similarly, one can obtain mixtures of1,2-benzacridonyl trianthrimides by using one or a mixture of theisomeric 1,2-benZacridonyl-5- or 8-aminoanthraquinones with one or amixture of the 1,5- and 1,8-dihalogenated anthraquinone in the foregoingcondensing reaction, as illustrated by the following example.

Example 5.-In place of 83 parts of 1,5-dichloranthraquinone employed inExample 1, there is employed the same weight of a mixture of about equalparts of 1,5- and 1,8-dichloranthraquinone, and in place of the1,2-benzacridcnyl-5-aminoanthraquinone employed in Example 1, there isemployed 102 parts of 1,2-benzacridonyl-8-aminoanthraquinone, otherconditions being the same as in Example 1. There is obtained as thefinal product a mixture of 1,2-benzacridonyl- 8,5, 1,1-trianthrimide and1,2-benzacridonyl 8,8, 1',1-trianthrimide. This mixture when heated forone-half hour with an aluminum chloride-sodium chloride mixture at14014=5,

as in Example 3, producesa dyestuff which dyes cotton somewhatbluershades than doesthc dyestuff obtained in Example 3, and ofsubstantially equal fastness.

In place of l-aminoanthraquinone there can be used1-N-acylamino-iaminoanthraduinone, or 1-N-acylamino-8-aminoanthraquinonein the above described condensations. Thus, instead of thel-aminoanthraquinone in Example 1, or its variations described above,1-N-benzoylamino-5- aminoanthraquinone or l-N-toluyl-5aminoanthraquinone or the correspondingl-N-acetylamino-8-aminoanthraquinone compounds may be used. If themiddle component is a diaminoanthraquinone, then 1-N-acy1amino-5- or 8-halogen anthraquinone compounds may be used to obtain the N-acylaminobenzacridonyl trianthrimide.

By fusions similar to those above described, ring closed condensationproducts can be made from other benzacridonyl trianthrimides whichcorrespond with the following general formula in which the imino groupsare attached to alpha positions and X is attached to an alpha positionand is hydrogen or acylamino; such as acetylamino, benzoylamino,toluylamino, etc.

The condensation products in such cases are dark powders, soluble inconcentrated sulfuric acid to form reddish-brown to Bordeaux-brownsolutions, which on dilution with Water precipitate typicalreddish-brown to yellow-brown flocks. The dyestuffs dye cotton from vatsin yellow-brown to red-brown shades which are characterized by excellentfastness to washing, chlorine, and light.

It will be realized by those skilled in the art that the invention isnot limited to the details of the above disclosure but that changes canbe made without departing from the scope of the invention.

Thus, the dianthrimides employed as intermediate products for theproduction of the trianthrimides in accordance with the presentinvention may be produced in other ways than those herein disclosed.Further, while, as above indicated, it is desirable to use substantiallyequimolecular proportions of the reacting ingredients, it is notessential that the amounts correspond exactly with such proportions.While the condensation of the aminoand halogen-anthraqulnone compoundswith each other, for the formation of the trianthrimides, is preferablycarried out with the aid of sodium carbonate and copper carbonate in thepresence of nitrobenzene as a solvent at temperatures ranging, forexample, from 190 to 210, the reaction may be carried out in thepresence of other organic solvents at other temperatures, for example,o-m'trotoluene at 190 to 222, and with the aid of other acid bindingagents, such as sodium acetate or ma nesium oxide, and other coppersalts, for example, copper oxide, copper acetate, etc., as catalysts.

I claim:

1. A brown vat dyestuff which in the form of a powder is a dark almostblack powder, very paringly soluble in organic solvents but dissolvingin concentrated sulfurio'a'cid to yield a violetbrown solution whichwhen diluted with water deposits the dyestufi' as Bordeaux-red toyellow-brown flocks, dyes cotton from a vat in reddish-brown toyellowish-brown shades of excellent fastness to washing, light, andchlorine, and is obtained by heating a trianthrimide selected from thegroup consisting of 1,2-benzacridonyl-5,5',1,1"-trianthrimide and1,2-benzacridonyl-8,8',l',1"-trianthrimide in the presence of anhydrousaluminum chloride at a final fusion temperature of between about C. andC. 2. The process of making a brown vat dyestuff which comprises heatingan anthrimide acridone compound of the following general formula:

in which the anthrimide imino groups are attached to alpha positions ofthe anthraquinone nuclei, and X is attached to an alpha position of theanthraquinone nucleus and is selected from the group consisting ofhydrogen and acylamino, in the presence of an acidic condensing agentselected from the group consisting of anhydrous aluminum chloride,ferric chloride, and zinc chloride.

3. The process of making a brown vat dyestuff which comprises heating ananthrimide compound of the following general formula:

in which the anthrimide imino groups are attached to alpha positions ofthe anthraquinone nuclei, and X is attached to an alpha position of theanthraquinone nucleus and is selected from the group consisting ofhydrogen and acylamino, in the presence of an acidic condensing agentselected from the group consisting of anhydrous aluminum chloride,ferric chloride, and zinc chloride at a final fusion temperatureoi'about 140" C. to about 145 C.

5. The process of making a brown vat dyestuff which comprises heating ananthrimide acridone compound of the following general formula in whichthe anthrimide imino groups are attached to alpha positions of theanthraquinone nuclei and X is an acylamino group attached to an alphaposition of the anthraquinone nucleus, in the presence of an acidiccondensing agent selected from the group consisting of anhydrousaluminum chloride, ferric chloride, and zinc chloride at a final fusiontemperature of about 90 C. to about 100 C.

6. A vat dyestufi obtained by reacting one molecular proportion of amixture of about equal weights of 1,5-dichloranthraquinone and1,8-dichloranthraquinone with about an equi-molecular proportion ofl-aminoanthraquinone, then reacting the resulting product, with about anequimolecular proportion of 1,2-benzacridonyl-8- aminoanthraquinone, andheating the resulting mixture of mono-1,2-benzacriclonyl trianthrimidesfor about one-half hour with an aluminum chloride-sodium chloridemixture at 140 to 145 C.

'7. The process of making a brown vat dyestufi which comprises heating areaction mixture containing anhydrous aluminum chloride and atrianthrimide selected from the g p Consistin of 1,2-benzacridonyl 5,5,1',1"- trianthrimide and 1,2-benzacridonyl-8,8',1,1-trianthrimide, at afinal fusion temperature of between 140 C. and 165 C.

8. The process of making a brown vat dyestuff which comprises heating areaction mixture containing anhydrous aluminum chloride and a mixture ofmono-1,2-benzacridonyl trianthrimides obtained by the interaction of1,2-benzacridonyl- B-aminoanthraquinone with the reaction product ofabout one molecular proportion of l-aminoanthraquinone and one molecularproportion of a mixture of 1,5-dichloranthraquinone and 1,8-dichloranthraquinone, at a final fusion temperature of about C. to aboutC.

9. The dyestuffs resulting from the fusion of an acidic ring closingcondensing agent with an anthrimide acridone compound of the followinggeneral formula:

in which the anthrimide imino groups are attached to alpha positions ofthe anthraquinone nuclei, and X is attached to an alpha position of theanthraquinone nucleus and is selected from the group consisting ofhydrogen and acylamino.

10. The dyestuffs resulting from the fusion of an acidic ring closingcondensing agent with an anthrimide acridone compound of the followinggeneral formula:

in which the anthrimide imino groups are attached to alpha positions ofthe anthraquinone nuclei.

11. The brown vat dyestufif resulting from the process of claim 8.

ALFRED MILLER.

